Polyene hydrocarbons containing two conjugated double bonds and process for obtaining same

ABSTRACT

There are provided novel polyene hydrocarbons containing two conjugated double bonds and having the following general formula   WHEREIN R is hydrogen or alkyl and R1, R2, R3, R4, R&#39;&#39;, R&#39;&#39;&#39;&#39; and R&#39;&#39;&#39;&#39;&#39;&#39; are hydrogen, alkyl or aryl.

United States Patent Arrighetti et al.

[ 51 July 11, 1972 [54] POLYENE HYDROCARBONS CONTAINING TWO CONJUGATED DOUBLE BONDS AND PROCESS FOR OBTAINING SAME [72] Inventors: Sergio Arrighetti, Milan; Eugenio Vajna; Sebastiano Cesca, both of San Donato Milanese, all of Italy [73] Assignee: Snam Progetti S.p.A., Milan, Italy [22] Filed: Jan. 22, 1971 [2]] Appl. No.: 109,009

[5 l Int. Cl. C07c 5/24 [58] Field of Search ..260/666 A, 666 FY [56] References Cited UNITED STATES PATENTS 3,347,875 10/1967 Foster ..260/666 PY 3,565,961 2/1971 Nagase et al ..260/666 PY 2,966,527 12/1960 Schmerling ..260/666 PY Primary Examiner-Delbert E. Gantz Assistant Examiner-Veronica OKeefe Attorney-Ralph M. Watson [57] ABSTRACT There are provided novel polyene hydrocarbons containing two conjugated double bonds and having the following general formula wherein R is hydrogen or alkyl and R,, R R R,, R, R" and R' are hydrogen, alkyl or aryl.

4 Claims, No Drawings in which R is hydrogen or an alkyl radical; R,, R R R R R" and R may be hydrogen, alkyl or aryl radicals.

These hydrocarbons are obtained by reacting a substituted or unsubstituted norbornene carbonyl derivative with a Grignard alkenyl derivative, for example according to the fol lowing scheme:

wherein R R R R R, R', R" and R have the aforesaid meanings and X is a halogen as Br, C1 or I.

It is also possible to react a substituted or unsubstituted Grignard compound of the norbomadiene halogen derivative with a ketone and then to dehydrate the corresponding alcohol, according to the scheme wherein R R R R R, R, R, R'" and X have the known meanings. Another unrestri'ctive example of the invention is the Diels-Alder reaction between the substituted or unsubstituted cyclopentadiene and an acetylene derivative containing at least a double bond adjacent to the triple bond:

R C=C Cal I 1 R! R!!! Its- All the above reactions are carried out at a temperature ranging from 0 to C, and preferably in the presence of a solvent which may be selected from ethers as tetrahydrofuran, dioxane, ethyl ether, butyl ether, and the like, from aromatic hydrocarbons as benzene, toluene, xylenes or mixtures of these solvents.

Typical unrestrictive examples of triene derivatives according to the present invention are the following ones:

2-propenyl-norbor-2,5-dieue II C H;

l :0 H--C H3 t C H: 2-(butenyl-2) 3-methyl-norbor-2, fi-dlene III CH! lsopropyliden-norbomadienyl-methane The invention is now illustrated by the following unrestrictive examples.

EXAMPLE I In a three neck flask provided with a reflux condenser and a mechanical stirrer, a tetrahydrofuran solution of decahydronorcanfor was added to a tetrahydrofuran 2M solution of the Gringard derivative of l-bromo-l-propene.

After a prudent mixing of the reactants, the reaction mass was allowed to reflow for 2 hours: then the magnesium salts were dissolved by an excess of a watery CH COOH (1:1 by volume), the organic phase was washed up to neutrality, dried on Ne so and the tetrahydrofuran was removed by distillation.

The remaining alcohol was already dehydrated during the distillation at reduced pressure (0.5 mmHg); in such a way the product I was obtained, having a b.p. 45 C/lO mmHg and a MW 132 (mass spectometry).

EXAMPLE [I The condensation product of cyclopentadiene with alphabromo-acrolein was dehydroalogenated into formylnorbornadiene. This compound was prudently treated with an excess of the Grignard reactant of Z-bromo-propane. The alcohol, obtained from the reaction mass according to the preceding example, was dehydrated on 01 A1 0, at 230 C and a product was obtained having a boiling point of 55 C at 10 mmI-IG, a molecular weight equal to 146 (mass spectrometry), it being in agreement with the structure III.

EXAMPLE II] By employing suitable catalyst [according to Dt. Botz, C. Bucur, J. Primus, L. Stanescu, D. Sandulescu-Rev. Chimi (Budarest) 12, 503 (1961) CA. 56 5848 g (1962) and to RP. 1,364,969] cyclopentadiene was allowed to react with 3- methyl-2-esen-4-ino at 144 C: the obtained produce was rectified and the compound II was obtained showing a well agreement with the proposed structure at the physical-chemical investigation.

What we claim is:

1. Polyene hydrocarbons containing two conjugated double bonds and having the following general formula:

in which R is hydrogen or an alkyl radical; R,, R R R R, R" and R' are hydrogen, alkyl or aryl radicals.

2. A process for preparing polyene hydrocarbons as claimed in claim 1 characterized in that a carbonyl derivative as:

is allowed to react with an alkenyl Grignard derivative as:

4 IR! Ila/I XMg-C=CR wherein R R,, R R, R, R, R" and R' have the aforesaid meanings; and X is a halogen as Cl, Br or I.

3. A process for preparing polyene hydrocarbons as claimed in claim 1 characterized in that said hydrocarbons are obtained by reacting a Grignard derivative as:

wherein R, R R R R R, R", R and X have the aforesaid meanings.

4. A process for preparing polyene hydrocarbons as claimed in claim 1 characterized in that cyclopentadiene is allowed to react with an acetylene derivative containing at least a double bond conjugated with the triple bond.

mg UNITED STATES PATM 0mm @E'NFMATE @F QQRREWWN Patent No. 3,676,511 Dated July 11 197 Inventor) Sergio Arrighetti, et a].

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby correctco ao shown below:

Column 1, line 45, correct the second formula as follows:

iv I HC I o c R" Colman 2, line 7 4, change "produce" to --product--='.

Column 4, line 4, after "R correct "R", first occurrence,

Signed and sealed this 19th day of February 197M.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. Q MARSHALL DANN Attesting Officer Commissioner of Patents 

2. A process for preparing polyene hydrocarbons as claimed in claim 1 characterized in that a carbonyl derivative as:
 3. A process for preparing polyene hydrocarbons as claimed in claim 1 characterized in that said hydrocarbons are obtained by reacting a Grignard derivative as:
 4. A process for preparing polyene hydrocarbons as claimed in claim 1 characterized in that cyclopentadiene is allowed to react with an acetylene derivative containing at least a double bond conjugated with the triple bond. 